Crystalline transition metal molybdotungstate

ABSTRACT

A hydroprocessing catalyst has been developed. The catalyst is a crystalline transition metal molybdotungstate material or metal sulfides derived therefrom, or both. The hydroprocessing using the crystalline transition metal molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from U.S. Provisional Application No.62/550,207 filed Aug. 25, 2017, the contents of which cited applicationare hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a new hydroprocessing catalyst. Moreparticularly this invention relates to a crystalline transition metalmolybdotungstate and its use as a hydroprocessing catalyst.Hydroprocessing may include hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

BACKGROUND

In order to meet the growing demand for petroleum products there isgreater utilization of sour crudes, which when combined with tighterenvironmental legislation regarding the concentration of nitrogen andsulfur within fuel, leads to accentuated refining problems. The removalof sulfur (hydrodesulfurization—HDS) and nitrogen(hydrodenitrification—HDN) containing compounds from fuel feed stocks istargeted during the hydrotreating steps of refining and is achieved bythe conversion of organic nitrogen and sulfur to ammonia and hydrogensulfide respectively.

Since the late 1940s the use of catalysts containing nickel (Ni) andmolybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfurremoval. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad,Division of Petroleum Chemistry, 115^(th) Meeting ACS, San Francisco,1949. For several decades now there has been an intense interestdirected towards the development of materials to catalyze the deepdesulfurization, in order to reduce the sulfur concentration to the ppmlevel. Some recent breakthroughs have focused on the development andapplication of more active and stable catalysts targeting the productionof feeds for ultra low sulfur fuels. Several studies have demonstratedimproved HDS and HDN activities through elimination of the support suchas, for example, Al₂O₃. Using bulk unsupported materials provides aroute to increase the active phase loading in the reactor as well asproviding alternative chemistry to target these catalysts.

More recent research in this area has focused on the ultra deepdesulfurization properties achieved by a Ni—Mo/W unsupported‘trimetallic’ material reported in, for example, U.S. Pat. No.6,156,695. The controlled synthesis of a broadly amorphous mixed metaloxide consisting of molybdenum, tungsten and nickel, significantlyoutperformed conventional hydrotreating catalysts. The structuralchemistry of the tri-metallic mixed metal oxide material was likened tothe hydrotalcite family of materials, referring to literature articlesdetailing the synthesis and characterization of a layered nickelmolybdate material, stating that the partial substitution of molybdenumwith tungsten leads to the production of a broadly amorphous phasewhich, upon decomposition by sulfidation, gives rise to superiorhydrotreating activities.

The chemistry of these layered hydrotalcite-like materials was firstreported by H. Pezerat, contribution à l'étude des molybdates hydratesde zinc, cobalt et nickel, C. R. ACAD. SCI., 261, 5490, who identified aseries of phases having ideal formulas MMoO₄.H₂O, EHM₂O⁻(MoO₄)₂.H₂O, andE_(2-x)(H₃O)_(x)M₂O(MoO₄)₂ where E can be NH₄ ⁺, Na⁺ or K⁺ and M can beZn²⁺, Co²⁺ or Ni²⁺.

Pezerat assigned the different phases he observed as being Φc, Φy or Φyand determined the crystal structures for Φx and Φy, however owing to acombination of the small crystallite size, limited crystallographiccapabilities and complex nature of the material, there were doubtsraised as to the quality of the structural assessment of the materials.During the mid 1970s, Clearfield et al attempted a more detailedanalysis of the Φx and Φy phases, see examples A. Clearfield, M. J.Sims, R. Gopal, INORG. CHEM., 15, 335; A. Clearfield, R. Gopal, C. H.Saldarriaga-Molina, INORG. CHEM., 16, 628. Single crystal studies on theproduct from a hydrothermal approach allowed confirmation of the Φxstructure, however they failed in their attempts to synthesize Φy andinstead synthesized an alternative phase, Na—Cu(OH)(MoO₄), see A.Clearfield, A. Moini, P. R. Rudolf, INORG. CHEM., 24, 4606.

The structure of Φy was not confirmed until 1996 when by Ying et al.Their investigation into a room temperature chimie douce synthesistechnique in the pursuit of a layered ammonium zinc molybdate led to ametastable aluminum-substituted zincite phase, prepared by thecalcination of Zn/Al layered double hydroxide (Zn₄Al₂(OH)₁₂CO₃.zH₂O).See example D. Levin, S. L. Soled, J. Y. Ying, INORG. CHEM., 1996, 35,4191-4197. This material was reacted with a solution of ammoniumheptamolybdate at room temperature to produce a highly crystallinecompound, the structure of which could not be determined throughconventional ab-initio methods. The material was indexed, yieldingcrystallographic parameters which were the same as that of an ammoniumnickel molybdate, reported by Astier, see example M. P. Astier, G. Dji,S. Teichner, J. ANN. CHIM. (Paris), 1987, 12, 337, a material belongingto a family of ammonium-amine-nickel-molybdenum oxides closely relatedto Pezerat's materials. Astier did not publish any detailed structuraldata on this family of materials, leading to Ying et al reproducing thematerial to be analyzed by high resolution powder diffraction in orderto elucidate the structure. Ying et al named this class of materials‘layered transition-metal molybdates’ or LTMs.

SUMMARY OF THE INVENTION

A crystalline transition metal molybdotungstate material has beenproduced and optionally sulfided, to yield an active hydroprocessingcatalyst. The crystalline transition metal molybdotungstate material hasa unique x-ray powder diffraction pattern showing peaks at 6.2, 3.5 and3.1 Å. The crystalline transition metal molybdotungstate material hasthe formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x’ varies from 0.001 to 2, or from 0.01to 1, or from 0.1 to 0.5; ‘y’ varies from 0.4 to 3, or from 0.5 to 2 orfrom 0.6 to 1; ‘z’ is a number which satisfies the sum of the valency ofM, x and y; the material is further characterized by a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment involves a method of making a crystalline transitionmetal molybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, Sn, Sb, Ti,Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from 0.5to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from 0.01to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by aunique x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A:

TABLE A d (Å) I/I₀ (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 mwherein the method comprises: forming a reaction mixture containingwater, a source of M, a source of Mo, source of W, and optionally asolubilizing agent, complexing agent, chelating agent, or a mixturethereof; optionally removing a component from the reaction mixture togenerate an intermediate reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand a portion of the water; reacting the reaction mixture or theintermediate mixture at a temperature from about 25° C. to about 500° C.for a period of time from about 30 minutes to 14 days to generate thecrystalline transition metal molybdotungstate material; and recoveringthe crystalline transition metal molybdotungstate material.

Yet another embodiment involves a conversion process comprisingcontacting a sulfiding agent with a material to generate metal sulfideswhich are contacted with a feed at conversion conditions to generate atleast one product, the material comprising: a crystalline transitionmetal molybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, Sn, Sb, Ti,Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from 0.5to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from 0.01to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by aunique x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A:

TABLE A d (Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Additional features and advantages of the invention will be apparentfrom the description of the invention, FIGURE and claims providedherein.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is the x-ray powder diffraction pattern of a crystallinetransition metal molybdotungstate prepared by the method as described inthe examples.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a crystalline transition metalmolybdotungstate composition and a process for preparing thecomposition. The material has the designation UPM-19. This compositionhas an empirical formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y.

The crystalline composition of the invention is characterized by havingan extended network of M-O-M, where M represents a metal, or combinationof metals listed above. The structural units repeat itself into at leasttwo adjacent unit cells without termination of the bonding. Thecomposition can have a one-dimensional network, such as, for example,linear chains.

The crystalline transition metal molybdotungstate composition is furthercharacterized by a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A.

TABLE A d (Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

The crystalline transition metal molybdotungstate composition of theinvention is yet further characterized by the x-ray powder diffractionpattern shown in the FIGURE.

The crystalline transition metal molybdotungstate composition can beprepared by solvothermal crystallization of a reaction mixture,typically by mixing reactive sources of molybdenum and tungsten with theappropriate source of metal ‘M’. Depending upon the metals sourcesselected, the reaction mixture may optionally include a solubilizingagent “SA” in order to facilitate the dissolution of the metals. Thereaction mixture may also optionally include a complexing agent, achelating agent, or both a complexing agent and a chelating agent “CA”in order to react with the metals prior to formation of the product.

Specific examples of suitable molybdenum sources include but are notlimited to molybdenum trioxide, ammonium dimolybdate, ammoniumthiomolybdate, and ammonium heptamolybdate. Suitable specific examplesof the tungsten source include but are not limited to tungsten trioxide,ammonium ditungstate, ammonium thiotungstate, ammonium heptatungstate,ammonium paratungstate, tungstic acid, tungsten oxytetrachloride,tungsten hexachloride, hydrogen tungstate, sodium ditungstate, sodiummetatungstate, sodium paratungstate and ammonium metatungstate. Sourcesof other metals “M” include but are not limited to the respectivehalide, acetate, nitrate, carbonate, thiols and hydroxide salts.Specific examples include nickel chloride, cobalt chloride, nickelbromide, zinc chloride, copper chloride, iron chloride, magnesiumchloride, cobalt bromide, magnesium chloride, nickel nitrate, cobaltnitrate, iron nitrate, manganese nitrate, zinc nitrate, copper nitrate,iron nitrate, nickel acetate, cobalt acetate, iron acetate, copperacetate, zinc acetate, nickel carbonate, cobalt carbonate, zinccarbonate, manganese carbonate, copper carbonate, iron carbonate, nickelhydroxide, cobalt hydroxide, manganese hydroxide, copper hydroxide, zinchydroxide, titanium oxide, manganese oxide, copper oxide, zinc oxide,cobalt oxide, nickel oxide, iron oxide, titanium tetrachloride, tinsulfate, zinc sulfate, iron sulfate, tin chloride pentahydrate, antimonychloride, antimony acetate, vanadium chloride.

Specific examples of the optional solubilizing agent “SA” include, butare not limited to, organic acids such as citric acid, malic acid,maleic acid, aliphatic acids; mineral acids such as sulfuric acid,hydrochloric acid, nitric acid, phosphoric acid and boric acid. Specificexamples of the optional complexing or chelating agents include, but arenot limited to, ammonium hydroxide, ammonium carbonate, ammoniumbicarbonate, ammonium chloride, ammonium fluoride,ethylenediaminetetraacetic acid, ethylenediamine, methylamine,dimethylamine or a combination thereof.

Generally, the solvothermal process used to prepare the composition ofthis invention involves forming a reaction mixture wherein all of thesources of the metal components, such as for example, Ni, Mo and W aremixed together, with the optional addition of either a solubilizingagent or a complexing agent or both. The reaction may be at ambienttemperatures or at elevated temperatures. The pressure may beatmospheric pressure or autogenous pressure. The vessel used may be aclosed vessel or an open vessel. In one embodiment, the reactants arethen mixed intermittently at elevated temperatures.

By way of specific examples, a reaction mixture may be formed which interms of molar ratios of the oxides is expressed by the formula:

MO_(x):AMoO_(y):BWO_(z):C(SA):D(CA):H₂O

where ‘M’ is selected from the group consisting of iron, cobalt, nickel,manganese, vanadium, copper, zinc, tin, titanium, zirconium, antimonyand mixtures thereof; ‘x’ is a number which satisfies the valency of‘M’; ‘A’ represents the ratio of ‘Mo’ relative to ‘M’ and varies from0.0001 to 0.75, or from 0.01 to 0.6, or from 0.1 to 0.4; ‘y’ is a numbersatisfies the valency of ‘Mo’; ‘B’ represents the ratio of ‘W’ relativeto ‘M’ and varies from 0.3999 to 2.4999, or from 0.5 to 2, or from 0.7to 1.25; ‘z’ is a number satisfies the valency of ‘W’; ‘C’ representsthe ratio of the solubilizing agent (SA) relative to ‘M’ and varies from0 to 50, or from 0.1 to 25, or from 1 to 10; ‘D’ represents the ratio ofthe complexing agent (CA) relative to ‘M’ and varies from 0 to 100, orfrom 0.1 to 50, or from 5 to 20; the ratio of H₂O and varies from 0.1 to1000, or from 1 to 100, or from 2 to 20. If required, the startingreagents may be pretreat be either the addition of a complexing agentsuch as, but not limited to, ammonium hydroxide or citric acid.Depending upon the metal reagents selected, the pH of the mixture mayadjusted to an acidic or basic regime. The pH of the mixture may beadjusted through the addition of a base such as NH₄OH, quaternaryammonium hydroxides, amines, and the like, or conversely be a mineralacid such as nitric acid, hydrochloric acid, sulfuric acid hydrofluoricacid, or an organic acid such as citric acid or malic acid.

In one embodiment, an intermediate reaction mixture may be formed byremoving a component of the reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand at least a portion of the water mixture. The intermediate may thenreacted as the reaction mixture at a temperature from about 25° C. toabout 500° C. for a period of from about 30 minutes to 14 days togenerate the crystalline transition metal molybdotungstate compositions.

Once the reaction mixture is formed, the reaction mixture is reacted attemperatures ranging from about 25° C. to about 500° C. for a period oftime ranging from 30 minutes to around 14 days. In one embodiment, thetemperate range for the reaction is from about 300° C. to about 400° C.and in another embodiment the temperature is in the range of from about100° C. to about 200° C. In one embodiment, the reaction time is fromabout 4 to about 6 hours, and in another embodiment the reaction time isfrom about 4 to 7 days. The reaction is carried out under atmosphericpressure in an open vessel or in a sealed vessel under autogenouspressure. The crystalline transition metal molybdotungstate compositionsare recovered as the reaction product. The crystalline transition metalmolybdotungstate compositions are characterized by their unique x-raypowder diffraction pattern as shown in Table A above and in the FIGURE.

Once formed, the crystalline transition metal molybdotungstate may havea binder incorporated, where the binder may be, for example, silicas,aluminas, silica aluminas, and mixtures thereof. The selection of binderincludes but is not limited to, anionic and cationic clays such ashydrotalcites, pyroaurite-sjogrenite-hydrotalcites, montmorillonite andrelated clays, kaolin, sepiolites, silicas, aluminas such as (pseudo)boehomite, gibbsite, flash calcined gibbsite, eta-alumina, zicronica,titania, alumina coated titania, silica-alumina, silica coated alumina,alumina coated silicas and mixtures thereof, or other materialsgenerally known as particle binders in order to maintain particleintegrity. These binders may be applied with or without peptization. Thebinder may be added to the bulk crystalline transition metalmolybdotungstate composition, and the amount of binder may range fromabout 1 to about 30 wt % of the finished catalysts or from about 5 toabout 26 wt % of the finished catalyst. The binder may be chemicallybound to the crystalline transition metal molybdotungstate composition,or may be present in a physical mixture with the crystalline transitionmetal molybdotungstate composition.

At least a portion of the crystalline transition metal molybdotungstatecomposition, with or without a binder, or before or after inclusion of abinder, can be sulfided in situ in an application or pre-sulfided toform metal sulfides which in turn are used in an application as acatalyst. The sulfidation may be conducted under a variety ofsulfidation conditions such as through contact of the crystallinetransition metal molybdotungstate composition with a sulfiding agentsuch as sulfur-containing stream or feedstream, or a gaseous mixture ofH₂S/H₂, or both. The sulfidation of the crystalline transition metalmolybdotungstate composition may be performed at elevated temperatures,typically ranging from about 50° C. to about 600° C., or from about 150°C. to about 500° C., or from about 250° C. to about 450° C. Thematerials resulting from the sulfiding step, the decomposition products,are referred to as metal sulfides which can be used as catalysts inconversion processes. As noted above, at least a portion of the metalsulfides may be present in a mixture with at least one binder. Thesulfiding step can take place at a location remote from other synthesissteps, remote from the location of the conversion process, or remotefrom both the location of synthesis and remote from location of theconversion process.

As discussed, at least a portion of the crystalline transition metalmolybdotungstate composition can be sulfided and the resulting metalsulfides may be used as a catalyst or catalyst support in conversionprocesses such as various hydrocarbon conversion processes.Hydroprocessing processes is one class of hydrocarbon conversionprocesses in which the crystalline transition metal molybdotungstatematerial is useful as a catalyst. Examples of specific hydroprocessingprocesses are well known in the art and include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. In one embodiment, a conversion process comprisescontacting the crystalline mixed transition metal tungstate with asulfiding agent to generate metal sulfides which are contacted with afeed stream at conversion conditions to generate at least one product.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Time with which the feed is incontact with the active catalyst, referred to as liquid hour spacevelocities (LHSV), should be in the range of about 0.1 h⁻¹ to about 10h⁻¹, or about 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets of these rangesmay be employed depending upon the feedstock being used. For example,when hydrotreating a typical diesel feedstock, operating conditions mayinclude from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about410° C., from about 0.25/h to about 5/h, and from about 84 Nm³ H₂/m³ toabout 850 Nm³ H₂/m³ feed. Other feedstocks may include gasoline,naphtha, kerosene, gas oils, distillates, and reformate.

Any of the lines, conduits, units, devices, vessels, surroundingenvironments, zones or similar used in the process or in the method ofmaking may be equipped with one or more monitoring components includingsensors, measurement devices, data capture devices or data transmissiondevices. Signals, process or status measurements, and data frommonitoring components may be used to monitor conditions in, around, andon process equipment. Signals, measurements, and/or data generated orrecorded by monitoring components may be collected, processed, and/ortransmitted through one or more networks or connections that may beprivate or public, general or specific, direct or indirect, wired orwireless, encrypted or not encrypted, and/or combination(s) thereof; thespecification is not intended to be limiting in this respect.

Signals, measurements, and/or data generated or recorded by monitoringcomponents may be transmitted to one or more computing devices orsystems. Computing devices or systems may include at least one processorand memory storing computer-readable instructions that, when executed bythe at least one processor, cause the one or more computing devices toperform a process that may include one or more steps. For example, theone or more computing devices may be configured to receive, from one ormore monitoring component, data related to at least one piece ofequipment associated with the process. The one or more computing devicesor systems may be configured to analyze the data. Based on analyzing thedata, the one or more computing devices or systems may be configured todetermine one or more recommended adjustments to one or more parametersof one or more processes described herein. The one or more computingdevices or systems may be configured to transmit encrypted orunencrypted data that includes the one or more recommended adjustmentsto the one or more parameters of the one or more processes or methodsdescribed herein.

Examples are provided below so that the invention may be described morecompletely. These examples are only by way of illustration and shouldnot be interpreted as a limitation of the broad scope of the invention,which is set forth in the claims.

Patterns presented in the following examples were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “I_(O)” being theintensity of the strongest line or peak, and “I” being the intensity ofeach of the other peaks. As will be understood by those skilled in theart the determination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. In some of the x-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, and w, which represent very strong, strong, medium,and weak, respectively. In terms of 100(I/I₀), the above designationsare defined as:

-   -   w=0.01-15, m=15-60: s=60-80 and vs=80-100.

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present. As willbe understood to those skilled in the art, it is possible for differentpoorly crystalline materials to yield peaks at the same position. If amaterial is composed of multiple poorly crystalline materials, then thepeak positions observed individually for each poorly crystallinematerial would be observed in the resulting summed diffraction pattern.Likewise, it is possible to have some peaks appear at the same positionswithin different, single phase, crystalline materials, which may besimply a reflection of a similar distance within the materials and notthat the materials possess the same structure.

Example 1

Ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) and ammoniumheptamolybdate tetrahydrate (5.3 g, 0.03 moles of Mo) were dissolved in150 ml of DI H₂O, concentrated ammonium hydroxide (25 mL, 30%) was addedto this solution. A second solution was prepared by adding nickelnitrate hexahydrate (43.62 g, 0.15 moles of Ni) to 150 ml of DI H₂O. Thetwo solutions were slowly mixed together over with the pH of the finalsolution being adjusted to pH 6.8 using a mild HNO₃ solution. Theprecipitated generated was isolated by filtration, washed with hot waterand then heat treated for using a ramp rate of 2° C. per hour until thetemperature reach 400° C. The material was kept at 300° C. for 24 hours.The resulting product was analyzed by X-ray powder diffraction, and theX-ray powder diffraction pattern is shown in the FIGURE.

Example 2

Using a ceramic dish, ammonium hydroxide (10 ml, 30%) was added tonickel carbonate hydrate (10.14 g, 0.1 moles of Ni) over a 30 minuteperiod. Ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) andammonium heptamolybdate tetrahydrate (1.76 g 0.01 moles of Mo) wereadded and the resultant mixture was mixed thoroughly and then heattreated for 12 hours at 150° C. with intermittent mixing. The mixturewas then heat treated further at 350° C. for 24 hours. The resultingproduct was analyzed by X-ray powder diffraction, and the X-ray powderdiffraction pattern is shown in the FIGURE.

Example 3

Using a ceramic dish, nickel nitrate hexahydrate (14.54 g, 0.05 moles ofNi), zinc nitrate hexahydrate (14.87 g, 0.05 moles of Zn), ammoniummetatungstate hydrate (17.71 g, 0.07 moles of W) and ammoniumheptamolybdate tetrahydrate (1.76 g 0.01 moles of Mo) were addedtogether and the resultant mixture was mixed thoroughly before beingheat treated for 12 hours at 150° C. with intermittent mixing. Themixture was then heat treated further at 350° C. for 24 hours. Theresulting product was analyzed by X-ray powder diffraction, and theX-ray powder diffraction pattern is shown in the FIGURE.

Example 4

Using a ceramic dish, nickel nitrate hexahydrate (29.75 g, 0.1 moles ofNi) and ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) andammonium heptamolybdate tetrahydrate (7.06 g 0.04 moles of Mo) wereadded together and the resultant mixture was mixed thoroughly beforebeing heat treated for 12 hours at 150° C. with intermittent mixing. Themixture was then heat treated further at 300° C. for 24 hours. Theresulting product was analyzed by X-ray powder diffraction, and theX-ray powder diffraction pattern is shown in the FIGURE.

Example 5

Nickel nitrate hexahydrate (100 g, 0.34 moles of Ni), zinc nitrate (3.63g, 0.03 moles of Zn), ammonium metatungstate hydrate (60.5 g, 0.24 molesof W), ammonium heptamolybdate tetrahydrate (1.76 g 0.01 moles of Mo)and ammonium carbonate (82.5 g, 0.86 moles) were mixed together in acovered beaker and heated at 50° C. for 4 days with intermittent mixing.The mixture was then transferred to a ceramic dish and was heated at 70°C. for 1 day, before being heated to 120° C. The mixture was then heatedfor 1 hour at 10° C. intervals from 120° C. to 190° C., after which thematerial was heated at 200° C. for 24 hrs. The resulting product wasanalyzed by X-ray powder diffraction, and the X-ray powder diffractionpattern is shown in the FIGURE.

Specific Embodiments

Embodiment 1 is a crystalline transition metal molybdotungstate materialhaving the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y; the material is further characterized by aunique x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A:

TABLE A d (Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment is the crystalline transition metal molybdotungstatematerial of embodiment 1 wherein the crystalline transition metalmolybdotungstate material is present in a mixture with at least onebinder and wherein the mixture comprises up to 25 wt-% binder.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein the binder is selected from the groupconsisting of silicas, aluminas, silica-aluminas, and mixtures thereof.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein M is nickel or cobalt.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein M is nickel.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein the crystalline transition metalmolybdotungstate material is sulfided.

Embodiment 2 is a method of making a crystalline transition metalmolybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y; the material is further characterized by aunique x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A:

TABLE A d (Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 mthe method comprising: (a) forming a reaction mixture containing water,a source of M, a source of Mo, a source of W, and optionally asolubilizing agent, complexing agent, chelating agent, or a mixturethereof; (b) optionally removing a component from the reaction mixtureto generate an intermediate reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand a portion of the water; (c) reacting the reaction mixture or theintermediate mixture at a temperature from about 25° C. to about 500° C.for a period of time from about 30 minutes to 14 days to generate thecrystalline transition metal molybdotungstate material; and (d)recovering the crystalline transition metal molybdotungstate material.

Another embodiment is the method of embodiment 2 wherein the recoveringis by filtration or centrifugation.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material furthercomprising adding a binder to the recovered crystalline transition metalmolybdotungstate material.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material wherein thebinder is selected from the group consisting of aluminas, silicas,alumina-silicas, and mixtures thereof.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material furthercomprising sulfiding the recovered crystalline transition metalmolybdotungstate material.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material wherein thereacting is conducted under atmospheric pressure or autogenous pressure.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material furthercomprising intermittent mixing during the reacting.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material wherein thetemperature is varied during the reacting.

Embodiment 3 is a conversion process comprising contacting a materialwith a sulfiding agent to convert at least a portion of the material tometal sulfides and contacting the metal sulfides with a feed atconversion conditions to generate at least one product, wherein thematerial comprises a crystalline transition metal molybdotungstatematerial having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y; the material is further characterized by aunique x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A:

TABLE A d (Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment is embodiment 3 wherein the conversion process ishydroprocessing.

Another embodiment is wherein the conversion process is selected fromthe group consisting of hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

Another embodiment is any of the previous conversion processes whereinthe crystalline transition metal molybdotungstate material is present ina mixture with at least one binder and wherein the mixture comprises upto about 25 wt-% binder.

Another embodiment is any of the previous conversion processes whereinthe crystalline transition metal molybdotungstate material is sulfided.

Another embodiment is embodiment 2 or 3 further comprising at least oneof: sensing at least one parameter of the process or method andgenerating a signal or data from the sensing; or generating andtransmitting a signal; or generating and transmitting data.

1. A crystalline transition metal molybdotungstate material having theformula:MMo_(x)W_(y)O_(z) where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn, Sn, Sb, Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4to 2.5; ‘x’ varies from 0.0001 to 0.75; ‘z’ is a number which satisfiesthe sum of the valency of M, x and y; the material is furthercharacterized by a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A: TABLE A d (Å) I/I0 (%) 6.20 s 3.52vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09 vs 1.93 m


2. The crystalline transition metal molybdotungstate material of claim 1wherein the crystalline transition metal molybdotungstate material ispresent in a mixture with at least one binder and wherein the mixturecomprises up to 25 wt-% binder.
 3. The crystalline transition metalmolybdotungstate material of claim 2 wherein the binder is selected fromthe group consisting of silicas, aluminas, and silica-aluminas.
 4. Thecrystalline transition metal molybdotungstate material of claim 1wherein M is nickel or cobalt.
 5. The crystalline transition metalmolybdotungstate material of claim 1 wherein M is nickel.
 6. Thecrystalline transition metal molybdotungstate material of claim 1wherein the crystalline transition metal molybdotungstate material issulfided.
 7. A method of making a crystalline transition metalmolybdotungstate material having the formula:MMo_(x)W_(y)O_(z) where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn, Sn, Sb, Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4to 2.5; ‘x’ varies from 0.0001 to 0.75; ‘z’ is a number which satisfiesthe sum of the valency of M, x and y; the material is furthercharacterized by a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A: TABLE A d (Å) I/I0 (%) 6.20 s 3.52vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09 vs 1.93 m

the method comprising: (a) forming a reaction mixture containing water,source of M, source of W, and optionally a solubilizing agent,complexing agent, chelating agent, or a mixture thereof; (b) optionallyremoving a component from the reaction mixture to generate anintermediate reaction mixture wherein the component is a precipitate, orat least a portion of the water, or both a precipitate and at least aportion of the water; (c) reacting the reaction mixture or theintermediate mixture at a temperature from about 25° C. to about 500° C.for a period of time from about 30 minutes to 14 days to generate thecrystalline transition metal molybdotungstate material; and (d)recovering the crystalline transition metal molybdotungstate material.8. The method of claim 7 wherein the recovering is by filtration orcentrifugation.
 9. The method of claim 7 further comprising adding abinder to the recovered crystalline transition metal molybdotungstatematerial.
 10. The method of claim 9 wherein the binder is selected fromthe group consisting of aluminas, silicas, alumina-silicas, and mixturesthereof.
 11. The method of claim 7 further comprising sulfiding therecovered crystalline transition metal molybdotungstate material. 12.The method of claim 7 wherein the reacting is conducted underatmospheric pressure or autogenous pressure.
 13. The method of claim 7further comprising intermittent mixing during the reacting.
 14. Themethod of claim 7 wherein the temperature is varied during the reacting.15. The method of claim 7 further comprising at least one of: sensing atleast one parameter of the process and generating a signal or data fromthe sensing; or generating and transmitting a signal; or generating andtransmitting data.
 16. A conversion process comprising contacting amaterial with a sulfiding agent to convert at least a portion of thematerial to metal sulfides and contacting the metal sulfides with a feedat conversion conditions to generate at least one product, wherein thematerial comprises a crystalline transition metal molybdotungstatematerial having the formula:MMo_(x)W_(y)O_(z) where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn, Sn, Sb, Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4to 2.5; ‘x’ varies from 0.0001 to 0.75; ‘z’ is a number which satisfiesthe sum of the valency of M, x and y; the material is furthercharacterized by a unique x-ray powder diffraction pattern showing peaksat the d-spacings listed in Table A: TABLE A d (Å) I/I0 (%) 6.20 s 3.52vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09 vs 1.93 m


17. The process of claim 16 wherein the conversion process ishydroprocessing.
 18. The process of claim 16 wherein the conversionprocess is selected from the group consisting of hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.
 19. The process of claim 16 wherein the crystallinetransition metal molybdotungstate material is present in a mixture withat least one binder and wherein the mixture comprises up to 25 wt-%binder.
 20. The process of claim 16 further comprising at least one of:sensing at least one parameter of the process and generating a signal ordata from the sensing; or generating and transmitting a signal; orgenerating and transmitting data.